SBR/unmodified HNT composites were prepared by open-mill mixing and vulcanization. The results showed that HNT could decrease the scorch and optimum cure time, and play a significant role in reinforcing SBR vulcanizates. Mechano-chemical grafting at the interface between HNT and SBR was investigated by using infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), solid-state 13C NMR spectra and bonded rubber content, etc. The results showed the shearing force during the mixing process can impel the grafting reaction of SBR onto the surfaces of HNT, which leads to interfacial chemical bonding between phenyl’s α-H of SBR and the surface groups of HNT with Si-OH or Al-OH. Thus, the mechanical properties of the composites were significantly enhanced.